CA1329625C - Process for urea production - Google Patents
Process for urea productionInfo
- Publication number
- CA1329625C CA1329625C CA000481820A CA481820A CA1329625C CA 1329625 C CA1329625 C CA 1329625C CA 000481820 A CA000481820 A CA 000481820A CA 481820 A CA481820 A CA 481820A CA 1329625 C CA1329625 C CA 1329625C
- Authority
- CA
- Canada
- Prior art keywords
- urea
- fresh
- ammonia
- carbamate
- urea composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/02—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds
- C07C273/04—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds from carbon dioxide and ammonia
Abstract
ABSTRACT
A process for the production of urea from ammonia and carbon dioxide via synthesis where the urea formation takes place in a synthesis zone (or zones) in which an excess of free ammonia is kept to favour high conversions, said synthesis zone (or zones) being followed by an ammonia separation and direct recycle to the reaction step, where the urea solution from said reaction zone (or zones) is intimately contacted for a short duration time with a minor portion of the fresh CO2.
The separation step is followed by a CO2 stripping step where the re-sidual carbamate is removed using a countercurrent fresh CO2 stream.
A process for the production of urea from ammonia and carbon dioxide via synthesis where the urea formation takes place in a synthesis zone (or zones) in which an excess of free ammonia is kept to favour high conversions, said synthesis zone (or zones) being followed by an ammonia separation and direct recycle to the reaction step, where the urea solution from said reaction zone (or zones) is intimately contacted for a short duration time with a minor portion of the fresh CO2.
The separation step is followed by a CO2 stripping step where the re-sidual carbamate is removed using a countercurrent fresh CO2 stream.
Description
IMPROVED PROCESS FOR UREA PRODUCTION 13 2 ~ 6 2 BACKGROUND OF THE INVENTION
1. Field of the Invention This invention relates to an improved process for the production of urea from ammonia and carbon dioxide via synthesis at adequate press-ure and temperature. The urea formation takes place in a synthesis zone (or zones) where an excess of free ammonia is kept to favour high conversions.
This improved process covers9in particular,a new treatment step to re-cover and recycle the unreacted materials (free ammonia and carbamate) from the reaction zone (or zones) in an optimal way to minimize energy consumption and investment costs.
1. Field of the Invention This invention relates to an improved process for the production of urea from ammonia and carbon dioxide via synthesis at adequate press-ure and temperature. The urea formation takes place in a synthesis zone (or zones) where an excess of free ammonia is kept to favour high conversions.
This improved process covers9in particular,a new treatment step to re-cover and recycle the unreacted materials (free ammonia and carbamate) from the reaction zone (or zones) in an optimal way to minimize energy consumption and investment costs.
2. Description of the Prior Art.
It is known that high reaction yields are favoured by a high ammonia excess (compared with the stoichiometric ratio) which require however a high reactor operating pressure and,asaconsequence,complex and energy consuming treatment sections downstream the reactor to remove and re-cycle said excess ammonia and the residual carbamate from the produced urea.
Some processes have been recently studied to minimize energy and investment requirement for the treatment sections downstream the reactor, but they are still complex and still require considerable amount of energy.
The USA patent 4208347 (Montedison), known as the I~R process (IsobaricDouble Recycle~, describes a two steps stripping treatment scheme where carbamate is removed with ammonia as stripping agent,in the first step, while free ammonia is removed with carbon dioxide as stripping agent,in the second step. A certain complexity of this scheme is evident.
The USA patent 4321410 (Mitsui Toatsu Chemicals and Toyo Engineering) known as the ACES process (Advanced Process for Cost and Energy Saving) describes a two steps stripping treatment performed in a newly designed stripper where the urea reactor effluent is contacted with the gases ~' 13~962~
(mainly NH3 and C02) coming from a falling film exchanger in an adiabatic first treatment step where free ammonia is removed and successively treated in the falling film exchanger (second treatment step) counter-currently with carbon dioxide introduced as stripping agent to remove the residual carbamate. With this process the amount of free ammonia that can be removed from the reactor effluent is limited due to the presence of NH3 in the gases contacting the urea solution in the adiabatic step, while a minimum content of free ammonia in the urea solution is desirable to obtain optimal carbamate removal in ~he subsequent C02 stripping step.
The Italian patent application 24357A/80 (Snamprogetti), published 1 June, 1981, describes a process very similar to the Montedison one but with the two treatment steps at different pressure (non isobaric). None of the above mentioned new processes achieve the direct recycle to the reactor of the free ammonia separated from the reactor effluent, which is optimal to minimize investment and energy consumption. The indirect recycle of ammonia in the downstrçam sections is made via acqueous solutions with the recycle of water in the reactor, which is detrimental for reaction yields The last generation processes, followed by the cited new generation ones, were dominated by the Stamicarbon C02 stripping and Snamprogetti NH~ stripping processes both using only one high pressure treatment step. In the Stamicarbon C0z stripping process, the reactor effluent with a low free ammonia content is directly treated in the C02 stripper to remove the residual carbamate. The content of ammonia in the reactor is kept low to have optimal carbamate separation in the CO2 stripper, but reaction yields are low with consequent high investment and energy consumption.
In the Snamprogetti NH3 stripping process, the reactor ~5 effluent with a higher free ammonia content is also directly treated in a "self stripping" treatment step to remove carbamate.
132~62~ 3 ' An important amount of free ammonia is still present in the urea sol-ution leaving the stripper and is separately recycled to the reactor using pumps.
This scheme implies the use of a rectifying column to separate pure G onia with high c06ts and energy consumption.
None of the last generation processes also achieves the direct recycle to the reactor of the free ammonia separated from the reactor effluents with minimum investment and energy consumption.
SUMMARY OF THE INVENTION
The direct recycle to the reaction zone of important amounts of ammonia is an optimal way of minimizing energy and investment costs which is ;
the main objective of the present invention.
It has been surprisingly discovered that important amounts of ammonia can be economically separated from the effluents of reactors operating with high excess ammonia and therefore with high conversion yields,ob-taining minimal excess of ammonia content in the urea solution which can be subsequently treated with maximum efficiency in a falling film exchanger with a counter-current of C02 stripping stream to remove the re-sidual carbamate.
Knowingly the presence of ammonia is detrimental to COz stripping efficiency.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The new process is described with reference to Fig. 1 which represents one of the possible embodiments of the invention.
,, ~, 132~625 - 3a -The aforesaid Figure 1 is one of a plurality of embodiments of the invention wherein a layer of appropriate mass transfer promoter is installed in separation equipment, the top part of which functions as a separator for evolving ammonia collection.
Figure 2 is a flow diagram illustrating an ammonia removal step located at the bottom part of a reactor wherein the layer of appropriate mass transfer promoter is installed in a reactor bottom empty space.
Figure 3 is an alternative ammonia removal step that is located in the bottom part of a reactor where a layer of appropriate mass transfer promoter is installed in a reactor bottom space with a relatively reduced diameter.
Figure 4 represents a flow diagram of the preferred embodiment of the invention in which adiabatic ammonia separation step is in intimate contact between a urea solution with excess ammonia with a fresh CO2 stream that is obtained in a very short time, by achieving a high mass transfer in a Venturi type mixer whereby evolved ammonia vapor is then separated from the urea solution in the separator.
The urea solution obtained in the high conversion yield reactor (R) with the presence therefore of a consistant amount of ammonia excess over the stoichiometric amount, is treated in the adiabatic step (S) where the major part of the excess ammonia is removed thanks to the intimate contact of the solution with a small amount of fresh CO2 fed to step (S) by line 1.
Line 2 feeds the urea solution from the reactor (R), which can be of conventional design, to the step (S), while the direct recycle of the separated excess ammonia from step (S) is made through line 3. The urea solution with minimum excess ammonia from step (S) is then fed (line 4) ~32~62~ 4-to a C02 stripper (ST), also of conventional design, where carbamate is removed with maximum efficiency in a falling film exchanger with counter-currentfreshC02 used as stripping agent introduced through line 5.
The vapors (mainly NH3 and C02 coming from carbamate decomposition) from stripper (ST) are fed through line 6 to the carbamate condenser (CC) where evolved heat is removed producing steam (line 7) utilized for the urea solution conventional treatment steps (not represented in the fig-ure) downstream stripper (ST).
The carbamate condenser (CC) receives also the carbamate solution (line8) from the above-mentioned,not represented,treatment steps and the inerts introduced with the C02 which are vented from reactor (R) (line 9). Said inerts, after removal in the carba~ate condenser (CC) of the residual N~3 and C02,are vented from the system (line 9).
The feed } onia (line 10) is partially sent (line 11) to the reactor after preheating,for reactor heat balance purposes,in preheater (P) and partially sent to the carb } te condenser (CC) (line 12).
Line 13 feeds the fresh C02,the major part of which is sent to the strip-per (ST) (line 5)-and a minor part is sent to step (S) (line 1).
The urea solution (line 14) after treatment in stripper (ST), with opti-mal residual content of carbamate, is finally sent to the conventional treatment steps to obtain the desired final urea product.
The carbamate solution from carbamate condenser (CC) is recycled to re-actor by gravity (line 15) It is critical that an intimate contact of short duration (a few seconds) between the urea solution with excess } onia and the introduced fresh C2 be obtained in the adiabatic } onia separation step (S). Figures 1, 2 and 3,where an appropriate layer of mass transfer promoter (L)(for ex.
rings or trays) is foreseen, represent different embodiments of the invention, where :
- in fig. 1 the layer of appropriate mass transfer promoter (L) is installed in a separate equipment (E) the top part of which (T) - 1329~2~ 5-functions as separator for the evolved ammonia collection. An appro-priate liquid distributor (D) is also foreseen;
- in Fig. 2 the ammonia removal step (S) is located in the bottom part of the reactor (R) where the layer (L) of appropriate mass transfer promoter is installed in a reactor bottom empty space (ES);
- in Fig. 3 the = onia removal step (S) is also located in the bottom part of the reactor (R), where the layer (L) of appropriate mass transfer promoter is installed in a reactor bottom empty space (ES) of reduced diameter.
Fig. 4 represents the preferred embodiment of the invention. In the adiabatic ammonia separation step (S) the intimate contact between the urea solution with excess ammonia (stream 2) and the introd~ced fresh C2 (stream 1) is obtained in a very short time,achieving a very high mass transfer,in a Venturi type mixer (VM). The evolved ammonia vapor is then separated from the urea solution in~the separator (ES).
The advantageous features of the invention can be evidenced by the fol-lowing comparison of the energy consumption (steam consumption in the loop) of the above mentioned known processes (last and new generation processes) with those of the examples describing the present invention.
The consumption figures of the known processes are taken from Dooyeweerd and Messen, Nitrogen issue n. 143 May 1983.
ACES Process (MT/TEC) : 474 kg of 22 bar steam for 1000 kg urea IDR Process (Montedison) : 524 kg of 22 bar steam for 1000 kg urea C2 Stripping(Stamicarbon): 633 kg of 18 bar steam for 1000 kg urea EXAMPLES 1 and 2 : lgO kg of 22 bar steam for 1000 kg urea EXAMPLE 3 : 150 kg of 8 bar steam for 1000 kg urea The features of the invention will be better illustrated by the follow-ing examples, where isobaric loops are described. The same improved re-sults can be obtained with schemes where the stripper (S) operates at lower pressure than the ammonia separation step (S).
132962a 6.
EX~PLE 1 Reference is made to Fig. 1,~3 and 4 (isobaric loop) eactor (R2 o~erati~ conditions - NH3/C02 molar ratio : 4.5 - H20/C02 molar ratio : 0.4 - temperature : 188C
- pressure : 180 bar - conversion rate (C02 to urea) : 74 %
Streams com~osition and ~uantities ________ __________ ________ - Stream (13) Fresh C02 :45 833 kg(100C) - Stream (1) Fresh C02 to the ammonia separation step (S) : 4.375 kg (100C) - Stream (5) Fresh C02 to the stripper (ST) :41.458 kg(100C) - Stream (10) Fresh NH3 :35.417 kg(25C) - Stream (2) Urea solution from reactor :NH3 72.250 kg 40.19 %
C2 16.125 kg 8.97 %
Urea 62.500 kg 34.77 %
H20 28.875 kg 16.07 %
179.750 kg100.00 %
Temperature 188C
132962~ 7.
- Stream (4) Vrea solution ~rom : NH329.750 kg 21.17 %
the ammonia separation step (S) C0220.000 kg 14.24 %
to the stripper (ST) Urea 62.500 kg 44.48 %
H2028.250 kg20.11 %
140.500 kglO0.00 %
Temperature : 191C
- Stream (3) Direct recycle of : NH3 42.500 kg 97.42 %
ammonia to the reactor (R) C02 500 kg l.t4 %
H20 625 kg1.44 Z
43.625 kg 100.00 %
Temperature : 190C
- Stream (14) Urea solution from : NH316.000 kg 12.98 %
the stripper (ST) C217.250 kg14.00 %
Urea 62.500 kg 51.71 %
H2027.500 kg22.31 %
123.250 kg100.00 Z
Temperature : 175C
132962~
, - Stream (6) NH3+C02 vapors : NH3 13.750 kg 23.43 %
from the stripper (ST) C2 44.208 kg 75.30 %
H2O 750 kg 1.27 %
58.708 kg 100.00 %
Temperature : 190C
- Stream (8) Carbamate solution : NH316~000 kg 38.10 %
from downstream sections C0217.250 kg41.07 ~
H208.750 kg20.83 %
42.000 kg100.00 %
Ener~y consumption - Steam consumption for stripper : l90 kg 22 bar steam for lO00 of (ST) of urea n the down~tream sections (not represented in the figure) for the re val and recycle of the residual NH3 and C02 contained in the urea solution coming from the C02 stripper, before final urea solution vacuum concentration to obtain finished product, the 6 to 7 bar steam produced in the carbamate condenser (CC) can be used. By the use of the technique of process to process direct heat recovery (multiple effect system) no extra steam will have to be im-ported from the plant battery limits.
1329625 ~.
E~'~LE 2 Reference is made to Fig. 1, 2, 3 and 4 (isobaric loop) Reactor (R) operating conditions - NH3/CO2 Molar Ratio : 4.5 - H2O/CO2 Molar Ratio : 0.4 - temperature : 188C
- pressure : 180 bar - conversion rate (C02 to urea) : 74 %
Streams composition and quantities ___________ ________ _ ___ ~ __ - Stream (13) Fresh C02 : 45.833 kg (100C) - Stream (1) Fresh CO2 to the ammonia separation step (S) :1.744 kg (100C) - Stream (5) Fresh CO2 to the stripper (ST) :44.084 kg (100C) - Stream (10) Fresh NH3 : 35.417 kg (25C) - Stream (2) Urea solution : NH3 72.250 kg 40.19 %
from reactor (R) C2 16.125 kg8.97 %
Urea 62.500 kg34.77 ~
H2O 28.875 kg16.07 %
179.750 kg100.00 Z
Temperature : 188C
132962~
10 .
- Stream (4) Urea solution from : NH353.519 kg 32.96 %
the ammonia separation step (S) C0217.669 kg 10,88 %
to the stripper (ST) Urea62.500 kg38.49 %
H2O28.687 kg17.67 %
t62.375 kg100.00 %
Temperature : 191C
- Stream (~) Direct recycle of : NH3 18.731 kg 97.97 %
ammonia to the reactor (R) C02 200 kg 1.05 %
H20 188 kg0.98 %
19.119 kg 100.00 %
Temperature : 190C
- Stream (14) Urea solution from : NH316.000 kg 12.98 %
the stripper (ST) ~~ C217.250 kg14.00 %
Urea62.500 kg50.71 %
H2027.500 kg22.31 %
123.250 kg100.00 %
Temperature : 175C
- Stream (6) NH3 ~ CO2 vapors : NH3 37.519 kg 45~09 %
from the stripper (ST)C2 44.508 kg 53.49 %
H2O 1.187 kg 1.42 %
83.214 kg 100.00 %
Temperature : 190C
132962a 1l.
- Stream t8) Carbamate solution : NH3 16.000 kg 38.10 %
from downstream sections C02 17.250 kg 41.07 %
H20 8.750 kg20.83 ~
42.000 kg100.00 %
Energ~ consu~tion See Example 1.
132962a 12.
Reference is made to Fig. 1-2-3 and 4 (isobaric loop).
Compared to example 2, operating conditions have been modified to have the stripper (ST) operating in adiabatic conditions.
In this case the stripper (ST) could be an apparatus different from a tube exchanger (ex.trays column) but to minimize residence time a falling film type tubes apparatus might still be the best choice as indicated in the figures.
_e_ctor _R) _p_r_t_ng _o_dit_ons - NH3/C02 molar ratio : 5 - H2C/C02 molar ratio : 0.5 - Temperature : 190 C
- Pressure : 200 bar - Conversion rate (C02 to urea) : 76 %
_treams composition and quantities_ _ _ _ _ _ _ _ _ _ _ _ _ - Stream (13) Fresh C02 :45.833 kg(100 C) - Stream (1) Fresh C02 to the ammonia separation step (S) :4.875 kg(100C) - Stream (5) Fresh C02 to the stripper (ST) :40.958 kg(100C) - Stream (10) Fresh NH3 :35.417 kg(25 C) - Stream (2) Urea solution from reactor :NH3 81.062 kg42.86 %
C2 14.500 kg 7.67 %
Urea 62.500 kg33.05 H20 31.063 kg16.42 %
189.125 kg 100.00 %
Temperature 190C
132962~ 13.
- Stream (4) Urea solution from : NH3 29.750 kg 21.03 %
the ammonia separation step (S) C02 18.875 kg 13.35 %
to the stripper (ST) Urea62.500 kg44.19 %
H2030.313 kg21.43 %
141.438 kg100.00 %
Temperature 192C
- Stream (9) Direct recycle of : NH3 51-312 kg 97.62 %
ammonia to the reactor (R) C02 500 kg 0.95 %
H20 750 kg1.43 %
52.562 kg 100.00 %
Temperature 191 C
- Stream (14) Urea solution from : NH3 20.625 kg 15.24 %
the stripper (ST) C222.500 kg16.63 %
Urea62.500 kg46.19 %
H2029.688 kg21.94 %
135.313 kg100.00 %
Temperature 165C
- Stream (6) NH3 + C02 vapors : NH3 9.125 kg 19.38 %
from the stripper (ST) C2 37~333 kg79.29 %
H20 625 kg1.33 %
47.083 kg 100.00 %
Temperature 192C
~ 3 ~ 9 6 2 ~ 14.
Energy consum~tion ____ ___ ____ ___ _ - Steam consumption for stripper (ST) : zero In the downstream sections (not represented in the figure) , for the removal and recycle of the higher residual NH3 and C02 contained in the urea solution coming from the C02 stripper, before final urea solution vacuum concentration to obtain finished product, the 7 to 8 bar steam produced in the carbamate condenser (CC) can be used.
By the use of the technique of process to process direct heat recovery (multiple effect system), a reduced amount of 150 kg for 1000 kg urea of 8 bar steam will have to be imported from the plant battery limits.
- 132962~ 15.
This example refers to the last generation Stamicarbon C02 stripping.
process modified according to the invention (see Fig. 1, 2, 3 and 4) in a case of a Stamicarbon C02 stripping plant modernization to reduce energy consumption.
Reactor (R) operating conditions ________________________________ - NH3/C02 molar ratio : 3.2 - H20/C02 molar ratio : 0.4 - Temperature : 184 C
- Pressure : 145 bar - Conversion rate (C02 to urea) : 62 %
Streams composition and ~uantities ___________ ____________ _________ - Stream (13) Fresh C02 : 45.833 kg (100C) - Stream (1) Fresh C02 to the ammonia separation step (S) : 2.112 kg (lO0 C) - Stream (5) Fresh C02 to the stripper (ST) : 43.721 kg (100 C) - Stream (10) Fresh NH3 : 35.417 kg (25 C) - Stream (2) Urea solution from reactor : NH356.000 kg31.55 %
C228.125 kg15.84 %
Urea 62.500 kg 35.21 %
H2030.875 kg17.40 %
177.500 kg100.00 %
Temperature 184 C
132~625 - Stream (4) Urea solution from : NH344.250 kg 26.44 %
the ammonia separation step (S) C02 30.037 kg 17.95 %
to the stripper (ST) Urea62.500 kg37.34 %
H2030.575 kg18.27 %
167.362 kg100.00 %
Temperature 185 C
- Stream (9) Direct recycle of :NH3 11.750 kg 95.92 %
= onia to the reactor (R) C02 200 kg1.63 %
H20 300 kg2.45 %
12.250 kg 100.00 %
Temperature 185C
- Stream (14) Urea solution from : NH3 9.133 kg 8.22 %
the stripper (ST) C210.846 kg9.77 %
Urea62.500 kg56.28 %
H2028.575 kg25.73 %
111.054 kg100.00 %
Temperature 170 C
- Stream (6) N~3 + C02 vapors : NH3 35.117 kg35.10 %
from the stripper (ST) C2 62.919 kg62.90 %
H20 2.000 kg2.00 %
100.036 kg 100.00 %
Temperature 185C
1329~25 17.
- Stream (8) Carbamate solution NH3 9.133 kg 30.64 %
from downstream sections C02 10.846 kg 36.39 %
H20 9.825 kg 32.97 %
29.804 kg 100.00 %
Energy Consumption The 22 bar steam consumption in the loop (C02 stripper) is reduced of 100 kg for 1000 kg urea with a modestinvestment for the installation of the ammonia separation step (S) This e~ample refers to the use of the invention for the revamping of the total or partial recycle conventional non stripping processes (Montedison, Mitsui Toatsu, etc), to reduce energy consumption.
With the use of the ammonia separation and direct ammonia recycle step (S), to treat the urea solution from the reactor, before the first de-composition step, a smaller quantity of ammonia and, as a consequence, of water, will have to be recycled in the downstream sections, improving reactor conversion yields with the reduction of water vaporization.
For both the above mentioned reasons (higher conversion yields and, conse-quently, less carbamate to be recycled and less vaporised water) a reduction of the 8 to 15Sbattery limits steam, of 300 kg per 1000 kg urea can be obtained.
This example refers to the use of the invention for the revamping of the Snamprogetti NH3 stripping plants, to reduce energy consumption and maintenance and operating costs.
With the use of the ammonia separation and recycle step (S), in this case located downstream the stripper, to remove the high e~cess ammonia content in the treated urea solution stream (the high e~cess ammonia of the urea solution from the reactor favours the NH3 self-stripping carbamate separation in the stripper), a smaller quantity of ammonia will have to be recycled in the downstream sections. The use of the rectifying column to separate and recycle pure ammonia with high costs and energy consumption, is so avoided.
It is known that high reaction yields are favoured by a high ammonia excess (compared with the stoichiometric ratio) which require however a high reactor operating pressure and,asaconsequence,complex and energy consuming treatment sections downstream the reactor to remove and re-cycle said excess ammonia and the residual carbamate from the produced urea.
Some processes have been recently studied to minimize energy and investment requirement for the treatment sections downstream the reactor, but they are still complex and still require considerable amount of energy.
The USA patent 4208347 (Montedison), known as the I~R process (IsobaricDouble Recycle~, describes a two steps stripping treatment scheme where carbamate is removed with ammonia as stripping agent,in the first step, while free ammonia is removed with carbon dioxide as stripping agent,in the second step. A certain complexity of this scheme is evident.
The USA patent 4321410 (Mitsui Toatsu Chemicals and Toyo Engineering) known as the ACES process (Advanced Process for Cost and Energy Saving) describes a two steps stripping treatment performed in a newly designed stripper where the urea reactor effluent is contacted with the gases ~' 13~962~
(mainly NH3 and C02) coming from a falling film exchanger in an adiabatic first treatment step where free ammonia is removed and successively treated in the falling film exchanger (second treatment step) counter-currently with carbon dioxide introduced as stripping agent to remove the residual carbamate. With this process the amount of free ammonia that can be removed from the reactor effluent is limited due to the presence of NH3 in the gases contacting the urea solution in the adiabatic step, while a minimum content of free ammonia in the urea solution is desirable to obtain optimal carbamate removal in ~he subsequent C02 stripping step.
The Italian patent application 24357A/80 (Snamprogetti), published 1 June, 1981, describes a process very similar to the Montedison one but with the two treatment steps at different pressure (non isobaric). None of the above mentioned new processes achieve the direct recycle to the reactor of the free ammonia separated from the reactor effluent, which is optimal to minimize investment and energy consumption. The indirect recycle of ammonia in the downstrçam sections is made via acqueous solutions with the recycle of water in the reactor, which is detrimental for reaction yields The last generation processes, followed by the cited new generation ones, were dominated by the Stamicarbon C02 stripping and Snamprogetti NH~ stripping processes both using only one high pressure treatment step. In the Stamicarbon C0z stripping process, the reactor effluent with a low free ammonia content is directly treated in the C02 stripper to remove the residual carbamate. The content of ammonia in the reactor is kept low to have optimal carbamate separation in the CO2 stripper, but reaction yields are low with consequent high investment and energy consumption.
In the Snamprogetti NH3 stripping process, the reactor ~5 effluent with a higher free ammonia content is also directly treated in a "self stripping" treatment step to remove carbamate.
132~62~ 3 ' An important amount of free ammonia is still present in the urea sol-ution leaving the stripper and is separately recycled to the reactor using pumps.
This scheme implies the use of a rectifying column to separate pure G onia with high c06ts and energy consumption.
None of the last generation processes also achieves the direct recycle to the reactor of the free ammonia separated from the reactor effluents with minimum investment and energy consumption.
SUMMARY OF THE INVENTION
The direct recycle to the reaction zone of important amounts of ammonia is an optimal way of minimizing energy and investment costs which is ;
the main objective of the present invention.
It has been surprisingly discovered that important amounts of ammonia can be economically separated from the effluents of reactors operating with high excess ammonia and therefore with high conversion yields,ob-taining minimal excess of ammonia content in the urea solution which can be subsequently treated with maximum efficiency in a falling film exchanger with a counter-current of C02 stripping stream to remove the re-sidual carbamate.
Knowingly the presence of ammonia is detrimental to COz stripping efficiency.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The new process is described with reference to Fig. 1 which represents one of the possible embodiments of the invention.
,, ~, 132~625 - 3a -The aforesaid Figure 1 is one of a plurality of embodiments of the invention wherein a layer of appropriate mass transfer promoter is installed in separation equipment, the top part of which functions as a separator for evolving ammonia collection.
Figure 2 is a flow diagram illustrating an ammonia removal step located at the bottom part of a reactor wherein the layer of appropriate mass transfer promoter is installed in a reactor bottom empty space.
Figure 3 is an alternative ammonia removal step that is located in the bottom part of a reactor where a layer of appropriate mass transfer promoter is installed in a reactor bottom space with a relatively reduced diameter.
Figure 4 represents a flow diagram of the preferred embodiment of the invention in which adiabatic ammonia separation step is in intimate contact between a urea solution with excess ammonia with a fresh CO2 stream that is obtained in a very short time, by achieving a high mass transfer in a Venturi type mixer whereby evolved ammonia vapor is then separated from the urea solution in the separator.
The urea solution obtained in the high conversion yield reactor (R) with the presence therefore of a consistant amount of ammonia excess over the stoichiometric amount, is treated in the adiabatic step (S) where the major part of the excess ammonia is removed thanks to the intimate contact of the solution with a small amount of fresh CO2 fed to step (S) by line 1.
Line 2 feeds the urea solution from the reactor (R), which can be of conventional design, to the step (S), while the direct recycle of the separated excess ammonia from step (S) is made through line 3. The urea solution with minimum excess ammonia from step (S) is then fed (line 4) ~32~62~ 4-to a C02 stripper (ST), also of conventional design, where carbamate is removed with maximum efficiency in a falling film exchanger with counter-currentfreshC02 used as stripping agent introduced through line 5.
The vapors (mainly NH3 and C02 coming from carbamate decomposition) from stripper (ST) are fed through line 6 to the carbamate condenser (CC) where evolved heat is removed producing steam (line 7) utilized for the urea solution conventional treatment steps (not represented in the fig-ure) downstream stripper (ST).
The carbamate condenser (CC) receives also the carbamate solution (line8) from the above-mentioned,not represented,treatment steps and the inerts introduced with the C02 which are vented from reactor (R) (line 9). Said inerts, after removal in the carba~ate condenser (CC) of the residual N~3 and C02,are vented from the system (line 9).
The feed } onia (line 10) is partially sent (line 11) to the reactor after preheating,for reactor heat balance purposes,in preheater (P) and partially sent to the carb } te condenser (CC) (line 12).
Line 13 feeds the fresh C02,the major part of which is sent to the strip-per (ST) (line 5)-and a minor part is sent to step (S) (line 1).
The urea solution (line 14) after treatment in stripper (ST), with opti-mal residual content of carbamate, is finally sent to the conventional treatment steps to obtain the desired final urea product.
The carbamate solution from carbamate condenser (CC) is recycled to re-actor by gravity (line 15) It is critical that an intimate contact of short duration (a few seconds) between the urea solution with excess } onia and the introduced fresh C2 be obtained in the adiabatic } onia separation step (S). Figures 1, 2 and 3,where an appropriate layer of mass transfer promoter (L)(for ex.
rings or trays) is foreseen, represent different embodiments of the invention, where :
- in fig. 1 the layer of appropriate mass transfer promoter (L) is installed in a separate equipment (E) the top part of which (T) - 1329~2~ 5-functions as separator for the evolved ammonia collection. An appro-priate liquid distributor (D) is also foreseen;
- in Fig. 2 the ammonia removal step (S) is located in the bottom part of the reactor (R) where the layer (L) of appropriate mass transfer promoter is installed in a reactor bottom empty space (ES);
- in Fig. 3 the = onia removal step (S) is also located in the bottom part of the reactor (R), where the layer (L) of appropriate mass transfer promoter is installed in a reactor bottom empty space (ES) of reduced diameter.
Fig. 4 represents the preferred embodiment of the invention. In the adiabatic ammonia separation step (S) the intimate contact between the urea solution with excess ammonia (stream 2) and the introd~ced fresh C2 (stream 1) is obtained in a very short time,achieving a very high mass transfer,in a Venturi type mixer (VM). The evolved ammonia vapor is then separated from the urea solution in~the separator (ES).
The advantageous features of the invention can be evidenced by the fol-lowing comparison of the energy consumption (steam consumption in the loop) of the above mentioned known processes (last and new generation processes) with those of the examples describing the present invention.
The consumption figures of the known processes are taken from Dooyeweerd and Messen, Nitrogen issue n. 143 May 1983.
ACES Process (MT/TEC) : 474 kg of 22 bar steam for 1000 kg urea IDR Process (Montedison) : 524 kg of 22 bar steam for 1000 kg urea C2 Stripping(Stamicarbon): 633 kg of 18 bar steam for 1000 kg urea EXAMPLES 1 and 2 : lgO kg of 22 bar steam for 1000 kg urea EXAMPLE 3 : 150 kg of 8 bar steam for 1000 kg urea The features of the invention will be better illustrated by the follow-ing examples, where isobaric loops are described. The same improved re-sults can be obtained with schemes where the stripper (S) operates at lower pressure than the ammonia separation step (S).
132962a 6.
EX~PLE 1 Reference is made to Fig. 1,~3 and 4 (isobaric loop) eactor (R2 o~erati~ conditions - NH3/C02 molar ratio : 4.5 - H20/C02 molar ratio : 0.4 - temperature : 188C
- pressure : 180 bar - conversion rate (C02 to urea) : 74 %
Streams com~osition and ~uantities ________ __________ ________ - Stream (13) Fresh C02 :45 833 kg(100C) - Stream (1) Fresh C02 to the ammonia separation step (S) : 4.375 kg (100C) - Stream (5) Fresh C02 to the stripper (ST) :41.458 kg(100C) - Stream (10) Fresh NH3 :35.417 kg(25C) - Stream (2) Urea solution from reactor :NH3 72.250 kg 40.19 %
C2 16.125 kg 8.97 %
Urea 62.500 kg 34.77 %
H20 28.875 kg 16.07 %
179.750 kg100.00 %
Temperature 188C
132962~ 7.
- Stream (4) Vrea solution ~rom : NH329.750 kg 21.17 %
the ammonia separation step (S) C0220.000 kg 14.24 %
to the stripper (ST) Urea 62.500 kg 44.48 %
H2028.250 kg20.11 %
140.500 kglO0.00 %
Temperature : 191C
- Stream (3) Direct recycle of : NH3 42.500 kg 97.42 %
ammonia to the reactor (R) C02 500 kg l.t4 %
H20 625 kg1.44 Z
43.625 kg 100.00 %
Temperature : 190C
- Stream (14) Urea solution from : NH316.000 kg 12.98 %
the stripper (ST) C217.250 kg14.00 %
Urea 62.500 kg 51.71 %
H2027.500 kg22.31 %
123.250 kg100.00 Z
Temperature : 175C
132962~
, - Stream (6) NH3+C02 vapors : NH3 13.750 kg 23.43 %
from the stripper (ST) C2 44.208 kg 75.30 %
H2O 750 kg 1.27 %
58.708 kg 100.00 %
Temperature : 190C
- Stream (8) Carbamate solution : NH316~000 kg 38.10 %
from downstream sections C0217.250 kg41.07 ~
H208.750 kg20.83 %
42.000 kg100.00 %
Ener~y consumption - Steam consumption for stripper : l90 kg 22 bar steam for lO00 of (ST) of urea n the down~tream sections (not represented in the figure) for the re val and recycle of the residual NH3 and C02 contained in the urea solution coming from the C02 stripper, before final urea solution vacuum concentration to obtain finished product, the 6 to 7 bar steam produced in the carbamate condenser (CC) can be used. By the use of the technique of process to process direct heat recovery (multiple effect system) no extra steam will have to be im-ported from the plant battery limits.
1329625 ~.
E~'~LE 2 Reference is made to Fig. 1, 2, 3 and 4 (isobaric loop) Reactor (R) operating conditions - NH3/CO2 Molar Ratio : 4.5 - H2O/CO2 Molar Ratio : 0.4 - temperature : 188C
- pressure : 180 bar - conversion rate (C02 to urea) : 74 %
Streams composition and quantities ___________ ________ _ ___ ~ __ - Stream (13) Fresh C02 : 45.833 kg (100C) - Stream (1) Fresh CO2 to the ammonia separation step (S) :1.744 kg (100C) - Stream (5) Fresh CO2 to the stripper (ST) :44.084 kg (100C) - Stream (10) Fresh NH3 : 35.417 kg (25C) - Stream (2) Urea solution : NH3 72.250 kg 40.19 %
from reactor (R) C2 16.125 kg8.97 %
Urea 62.500 kg34.77 ~
H2O 28.875 kg16.07 %
179.750 kg100.00 Z
Temperature : 188C
132962~
10 .
- Stream (4) Urea solution from : NH353.519 kg 32.96 %
the ammonia separation step (S) C0217.669 kg 10,88 %
to the stripper (ST) Urea62.500 kg38.49 %
H2O28.687 kg17.67 %
t62.375 kg100.00 %
Temperature : 191C
- Stream (~) Direct recycle of : NH3 18.731 kg 97.97 %
ammonia to the reactor (R) C02 200 kg 1.05 %
H20 188 kg0.98 %
19.119 kg 100.00 %
Temperature : 190C
- Stream (14) Urea solution from : NH316.000 kg 12.98 %
the stripper (ST) ~~ C217.250 kg14.00 %
Urea62.500 kg50.71 %
H2027.500 kg22.31 %
123.250 kg100.00 %
Temperature : 175C
- Stream (6) NH3 ~ CO2 vapors : NH3 37.519 kg 45~09 %
from the stripper (ST)C2 44.508 kg 53.49 %
H2O 1.187 kg 1.42 %
83.214 kg 100.00 %
Temperature : 190C
132962a 1l.
- Stream t8) Carbamate solution : NH3 16.000 kg 38.10 %
from downstream sections C02 17.250 kg 41.07 %
H20 8.750 kg20.83 ~
42.000 kg100.00 %
Energ~ consu~tion See Example 1.
132962a 12.
Reference is made to Fig. 1-2-3 and 4 (isobaric loop).
Compared to example 2, operating conditions have been modified to have the stripper (ST) operating in adiabatic conditions.
In this case the stripper (ST) could be an apparatus different from a tube exchanger (ex.trays column) but to minimize residence time a falling film type tubes apparatus might still be the best choice as indicated in the figures.
_e_ctor _R) _p_r_t_ng _o_dit_ons - NH3/C02 molar ratio : 5 - H2C/C02 molar ratio : 0.5 - Temperature : 190 C
- Pressure : 200 bar - Conversion rate (C02 to urea) : 76 %
_treams composition and quantities_ _ _ _ _ _ _ _ _ _ _ _ _ - Stream (13) Fresh C02 :45.833 kg(100 C) - Stream (1) Fresh C02 to the ammonia separation step (S) :4.875 kg(100C) - Stream (5) Fresh C02 to the stripper (ST) :40.958 kg(100C) - Stream (10) Fresh NH3 :35.417 kg(25 C) - Stream (2) Urea solution from reactor :NH3 81.062 kg42.86 %
C2 14.500 kg 7.67 %
Urea 62.500 kg33.05 H20 31.063 kg16.42 %
189.125 kg 100.00 %
Temperature 190C
132962~ 13.
- Stream (4) Urea solution from : NH3 29.750 kg 21.03 %
the ammonia separation step (S) C02 18.875 kg 13.35 %
to the stripper (ST) Urea62.500 kg44.19 %
H2030.313 kg21.43 %
141.438 kg100.00 %
Temperature 192C
- Stream (9) Direct recycle of : NH3 51-312 kg 97.62 %
ammonia to the reactor (R) C02 500 kg 0.95 %
H20 750 kg1.43 %
52.562 kg 100.00 %
Temperature 191 C
- Stream (14) Urea solution from : NH3 20.625 kg 15.24 %
the stripper (ST) C222.500 kg16.63 %
Urea62.500 kg46.19 %
H2029.688 kg21.94 %
135.313 kg100.00 %
Temperature 165C
- Stream (6) NH3 + C02 vapors : NH3 9.125 kg 19.38 %
from the stripper (ST) C2 37~333 kg79.29 %
H20 625 kg1.33 %
47.083 kg 100.00 %
Temperature 192C
~ 3 ~ 9 6 2 ~ 14.
Energy consum~tion ____ ___ ____ ___ _ - Steam consumption for stripper (ST) : zero In the downstream sections (not represented in the figure) , for the removal and recycle of the higher residual NH3 and C02 contained in the urea solution coming from the C02 stripper, before final urea solution vacuum concentration to obtain finished product, the 7 to 8 bar steam produced in the carbamate condenser (CC) can be used.
By the use of the technique of process to process direct heat recovery (multiple effect system), a reduced amount of 150 kg for 1000 kg urea of 8 bar steam will have to be imported from the plant battery limits.
- 132962~ 15.
This example refers to the last generation Stamicarbon C02 stripping.
process modified according to the invention (see Fig. 1, 2, 3 and 4) in a case of a Stamicarbon C02 stripping plant modernization to reduce energy consumption.
Reactor (R) operating conditions ________________________________ - NH3/C02 molar ratio : 3.2 - H20/C02 molar ratio : 0.4 - Temperature : 184 C
- Pressure : 145 bar - Conversion rate (C02 to urea) : 62 %
Streams composition and ~uantities ___________ ____________ _________ - Stream (13) Fresh C02 : 45.833 kg (100C) - Stream (1) Fresh C02 to the ammonia separation step (S) : 2.112 kg (lO0 C) - Stream (5) Fresh C02 to the stripper (ST) : 43.721 kg (100 C) - Stream (10) Fresh NH3 : 35.417 kg (25 C) - Stream (2) Urea solution from reactor : NH356.000 kg31.55 %
C228.125 kg15.84 %
Urea 62.500 kg 35.21 %
H2030.875 kg17.40 %
177.500 kg100.00 %
Temperature 184 C
132~625 - Stream (4) Urea solution from : NH344.250 kg 26.44 %
the ammonia separation step (S) C02 30.037 kg 17.95 %
to the stripper (ST) Urea62.500 kg37.34 %
H2030.575 kg18.27 %
167.362 kg100.00 %
Temperature 185 C
- Stream (9) Direct recycle of :NH3 11.750 kg 95.92 %
= onia to the reactor (R) C02 200 kg1.63 %
H20 300 kg2.45 %
12.250 kg 100.00 %
Temperature 185C
- Stream (14) Urea solution from : NH3 9.133 kg 8.22 %
the stripper (ST) C210.846 kg9.77 %
Urea62.500 kg56.28 %
H2028.575 kg25.73 %
111.054 kg100.00 %
Temperature 170 C
- Stream (6) N~3 + C02 vapors : NH3 35.117 kg35.10 %
from the stripper (ST) C2 62.919 kg62.90 %
H20 2.000 kg2.00 %
100.036 kg 100.00 %
Temperature 185C
1329~25 17.
- Stream (8) Carbamate solution NH3 9.133 kg 30.64 %
from downstream sections C02 10.846 kg 36.39 %
H20 9.825 kg 32.97 %
29.804 kg 100.00 %
Energy Consumption The 22 bar steam consumption in the loop (C02 stripper) is reduced of 100 kg for 1000 kg urea with a modestinvestment for the installation of the ammonia separation step (S) This e~ample refers to the use of the invention for the revamping of the total or partial recycle conventional non stripping processes (Montedison, Mitsui Toatsu, etc), to reduce energy consumption.
With the use of the ammonia separation and direct ammonia recycle step (S), to treat the urea solution from the reactor, before the first de-composition step, a smaller quantity of ammonia and, as a consequence, of water, will have to be recycled in the downstream sections, improving reactor conversion yields with the reduction of water vaporization.
For both the above mentioned reasons (higher conversion yields and, conse-quently, less carbamate to be recycled and less vaporised water) a reduction of the 8 to 15Sbattery limits steam, of 300 kg per 1000 kg urea can be obtained.
This example refers to the use of the invention for the revamping of the Snamprogetti NH3 stripping plants, to reduce energy consumption and maintenance and operating costs.
With the use of the ammonia separation and recycle step (S), in this case located downstream the stripper, to remove the high e~cess ammonia content in the treated urea solution stream (the high e~cess ammonia of the urea solution from the reactor favours the NH3 self-stripping carbamate separation in the stripper), a smaller quantity of ammonia will have to be recycled in the downstream sections. The use of the rectifying column to separate and recycle pure ammonia with high costs and energy consumption, is so avoided.
Claims (12)
1. In a process for the production of urea from ammonia and carbon dioxide at an effective pressure and temperature, wherein the urea formation takes place in at least one synthesis zone and in which an excess of free ammonia is present to favor high conversations, thereby producing a urea composition containing an excess of free ammonia, residual carbamate and urea and the residual carbamate is removed by stripping the urea composition with a counter current stream of a major amount of fresh CO2, the improvement comprising prior to contracting the urea composition with the major amount of fresh CO2, adiabatically contacting the urea composition with a minor amount of fresh CO2 to thereby remove an amount of NH3 from the urea composition which is substantially free of water vapor and directly recycling the NH3 to the synthesis zone.
2. In a process for the production of urea from ammonia and carbon dioxide at an effective pressure and temperature, wherein the urea formation takes place in at least one synthesis zone and in which an excess of free ammonia is present to favor high conversions, thereby producing a urea composition containing an excess of free ammonia, residual carbamate and urea and the residual carbamate is removed by stripping the urea composition with a counter current stream of a major amount of fresh CO2, the improvement comprising prior to contracting the urea composition with the major amount of fresh CO2, adiabatically contracting the urea composition with a minor amount of fresh CO2 to thereby remove an amount of NH3 from the urea composition which is substantially free of water vapor.
3. The process as claimed in claim 1 or 2 wherein the adiabatic contacting step is performed using a layer of an effective mass transfer promoter and the fresh CO2 flows counter-currently to the urea composition.
4. The process as claimed in claim 1 or 2 wherein the adiabatic contracting step is performed using a layer of an effective mass transfer promoter and the fresh CO2 flows counter-currently to the urea composition.
5. The process as claimed in claim 1 or 2 wherein the duration of contracting between the urea composition and the minor amount of fresh CO2 is less than about 10 seconds.
6. The process as claimed in claim 1 or 2 wherein the minor amount of CO2 is from about 4 to 12% by weight of total CO2.
7. The process as claimed in claim 1 or 2 wherein the minor amount of CO2 is less than about 20% by weight of total CO2.
8. The process as claimed in 1 or 2 wherein the stripping step operates in an adiabatic condition whereby any heat required for residual carbamate removal is supplied by a reduction heat produced by part of the major amount of fresh CO2 reacting with free ammonia to form carbamate.
9. The process as claimed in 1 or 2 wherein the synthesis zone operates at a pressure in the range of 120 to 250 kg/cm2.
10. The process as claimed in claim 1 or 2 wherein the NH3/CO2 molar ratio in the synthesis zone is in the range of 2.5 to 6.
11. The process as claimed in claim 1 or 2 wherein the stripping step operates at a lower pressure than the adiabatic contracting step.
12. The process as claimed in 1 or 2 wherein the stripping step operates in an adiabatic condition whereby any heat required for residual carbamate removal is supplied by a reduction heat produced by part of the major amount of fresh CO2 reacting with free ammonia to form carbamate and wherein the stripping step for removing residual carbamate is uses a falling film exchanger.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH2477/84-6 | 1984-05-19 | ||
| CH247784 | 1984-05-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1329625C true CA1329625C (en) | 1994-05-17 |
Family
ID=4234678
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000481820A Expired - Fee Related CA1329625C (en) | 1984-05-19 | 1985-05-17 | Process for urea production |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4613696A (en) |
| EP (1) | EP0180704B1 (en) |
| AT (1) | ATE37868T1 (en) |
| CA (1) | CA1329625C (en) |
| DE (1) | DE3565532D1 (en) |
| IN (1) | IN164714B (en) |
| SU (1) | SU1417794A3 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL8602769A (en) * | 1986-11-03 | 1988-06-01 | Stamicarbon | METHOD FOR CONCENTRATING A UREA SOLUTION AND APPARATUS FOR CARRYING OUT THE METHOD |
| US4869887A (en) * | 1987-10-30 | 1989-09-26 | Dijk Christiaan P Van | Integrated ammonia-urea process |
| US4988491A (en) * | 1989-04-11 | 1991-01-29 | Christiaan Van Dijk | Flexible integration of the production of ammonia and urea |
| US6150555A (en) * | 1992-05-08 | 2000-11-21 | Urea Casale, S.A. | Process for urea production |
| DE69326881D1 (en) * | 1993-01-07 | 1999-12-02 | Urea Casale Sa | Improved process for producing urea using a carbon dioxide removal step |
| NL1007713C2 (en) | 1997-12-05 | 1999-06-08 | Dsm Nv | Process for the preparation of urea. |
| EP1714959B1 (en) * | 2005-04-19 | 2015-11-18 | Casale Sa | Process for urea production and related plant |
| US7687041B2 (en) * | 2008-02-27 | 2010-03-30 | Kellogg Brown & Root Llc | Apparatus and methods for urea production |
| EP2128129A1 (en) * | 2008-05-20 | 2009-12-02 | Urea Casale S.A. | Method for the modernization of a urea production plant |
| EP2199279A1 (en) * | 2008-12-17 | 2010-06-23 | Urea Casale S.A. | Improvement to the high-pressure loop in a process for synthesis of urea |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NO150512C (en) * | 1977-05-05 | 1984-10-31 | Montedison Spa | PROCEDURE FOR MANUFACTURING UREA. |
| US4235816A (en) * | 1979-03-08 | 1980-11-25 | Snamprogetti S.P.A. | Integrated ammonia-urea process |
| JPS5811432B2 (en) * | 1979-10-08 | 1983-03-02 | 三井東圧化学株式会社 | Urea synthesis method |
| JPS56128749A (en) * | 1980-03-13 | 1981-10-08 | Mitsui Toatsu Chem Inc | Stripping of unreacted material in urea preparation process |
| US4311856A (en) * | 1980-12-31 | 1982-01-19 | Toyo Engineering Corp. | Process for synthesizing urea |
| IT1212524B (en) * | 1982-06-08 | 1989-11-30 | Montedison Spa | PROCESS PERFECTED FOR THE TRANSFER, FROM THE LIQUID PHASE TO THE GASEOUS PHASE, OF THE EXCESS AMMONIA CONTAINED IN AQUEOUS SOLUTIONS OF UREA. |
-
1985
- 1985-04-20 AT AT85104811T patent/ATE37868T1/en not_active IP Right Cessation
- 1985-04-20 EP EP85104811A patent/EP0180704B1/en not_active Expired
- 1985-04-20 DE DE8585104811T patent/DE3565532D1/en not_active Expired
- 1985-04-27 IN IN319/MAS/85A patent/IN164714B/en unknown
- 1985-05-02 US US06/729,528 patent/US4613696A/en not_active Expired - Lifetime
- 1985-05-17 SU SU853898059A patent/SU1417794A3/en active
- 1985-05-17 CA CA000481820A patent/CA1329625C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| SU1417794A3 (en) | 1988-08-15 |
| US4613696A (en) | 1986-09-23 |
| EP0180704A1 (en) | 1986-05-14 |
| EP0180704B1 (en) | 1988-10-12 |
| ATE37868T1 (en) | 1988-10-15 |
| IN164714B (en) | 1989-05-13 |
| DE3565532D1 (en) | 1988-11-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4208347A (en) | Process for the synthesis of urea | |
| US6852886B2 (en) | Process for the preparation of urea | |
| RU2196767C2 (en) | Method of combined production of ammonia and carbamide, plant for method embodiment, method of modernization of ammonia and carbamide synthesis plants | |
| US4053507A (en) | Method of recovering unreacted materials and heat in urea synthesis | |
| CA1329625C (en) | Process for urea production | |
| US4539077A (en) | Process for the preparation of urea | |
| AU2002303036A1 (en) | Process for the preparation of urea | |
| NO752079L (en) | ||
| EP0086805B1 (en) | Process for the preparation of urea | |
| US6392096B1 (en) | Process for the preparation of urea | |
| US6680407B2 (en) | Installation and process for the preparation of urea | |
| JPH0920746A (en) | Method for synthesizing urea in high yield | |
| EP0145054B1 (en) | Process for preparing urea | |
| US20010041813A1 (en) | Process for the preparation of urea | |
| CA2553388C (en) | Method for increasing the capacity of an existing urea process | |
| AU2006244735B2 (en) | Method for concentrating an aqueous ammonium carbamate stream | |
| CA2460516C (en) | Process for the preparation of urea | |
| EP0136764A2 (en) | Process for the preparation of urea | |
| EP4245755A1 (en) | Process for the production of high-purity melamine from urea pyrolysis, with reduced energy consumption and improved integration with the urea plant | |
| EP0822181B1 (en) | Process and plant for the production of urea with high conversion yield and low energy consumption | |
| RU2071467C1 (en) | Process for preparing carbamide | |
| CA2462288C (en) | Process for the preparation of urea | |
| EP0136765A2 (en) | Process for the preparation of urea |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |